---Energy level diagrams of diatomic

If we combine the splitting schemes for the 2s and 2p orbitals, we can predict bond order in all of
the diatomic molecules and ions composed of elements in the first complete row of the periodic
table. Remember that only the valence orbitals of the atoms need be considered; as we saw in the
cases of lithium hydride and dilithium, the inner orbitals remain tightly bound and retain their
localized atomic character. We now describe examples of systems involving period 2
homonuclear diatomic molecules, such as N2, O2, and F2.

FOUR KEY POINTS TO REMEMBER WHEN DRAWING MOLECULAR ORBITAL

DIAGRAMS:

1. The number of molecular orbitals produced is the same as the number of atomic orbitals
used to create them (the "law of conservation of orbitals").
2. As the overlap between two atomic orbitals increases, the difference in energy between
the resulting bonding and antibonding molecular orbitals increases.
3. When two atomic orbitals combine to form a pair of molecular orbitals, the bonding
molecular orbital is stabilized about as much as the antibonding molecular orbital is
destabilized.
4. The interaction between atomic orbitals is greatest when they have the same energy.

We illustrate how to use these points by constructing a molecular orbital energy-level diagram
for F2. We use the diagram in part (a) in Figure 9.8.19.8.1; the n = 1 orbitals (σ1s and σ1s*) are
located well below those of the n = 2 level and are not shown. As illustrated in the diagram, the
σ2s and σ2s* molecular orbitals are much lower in energy than the molecular orbitals derived from
the 2p atomic orbitals because of the large difference in energy between the 2s and 2p atomic
orbitals of fluorine. The lowest-energy molecular orbital derived from the three 2p orbitals on
each F is σ2pzσ2pz and the next most stable are the two degenerate
orbitals, π2pxπ2px and π2pyπ2py. For each bonding orbital in the diagram, there is an
antibonding orbital, and the antibonding orbital is destabilized by about as much as the
corresponding bonding orbital is stabilized. As a result, the σ⋆2pzσ2pz⋆ orbital is higher in
energy than either of the degenerate π⋆2pxπ2px⋆and π⋆2pyπ2py⋆ orbitals. We can now fill the
orbitals, beginning with the one that is lowest in energy.

Each fluorine has 7 valence electrons, so there are a total of 14 valence electrons in the
F2 molecule. Starting at the lowest energy level, the electrons are placed in the orbitals according
to the Pauli principle and Hund’s rule. Two electrons each fill the σ 2s and σ2s* orbitals, 2 fill
the σ2pzσ2pz orbital, 4 fill the two degenerate π orbitals, and 4 fill the two degenerate π * orbitals,
for a total of 14 electrons. To determine what type of bonding the molecular orbital approach
predicts F2 to have, we must calculate the bond order. According to our diagram, there are 8
bonding electrons and 6 antibonding electrons, giving a bond order of (8 − 6) ÷ 2 = 1. Thus F2 is
predicted to have a stable F–F single bond, in agreement with experimental data.
 Figure 9.8.19.8.1: Molecular Orbital Energy-Level Diagrams for Homonuclear Diatomic
Molecules.(a) For F2, with 14 valence electrons (7 from each F atom), all of the energy levels
except the highest, σ⋆2pzσ2pz⋆ are filled. This diagram shows 8 electrons in bonding orbitals
and 6 in antibonding orbitals, resulting in a bond order of 1. (b) For O2, with 12 valence
electrons (6 from each O atom), there are only 2 electrons to place in the (π⋆npx,π⋆npy)
(πnpx⋆,πnpy⋆) pair of orbitals. Hund’s rule dictates that one electron occupies each orbital, and
their spins are parallel, giving the O2 molecule two unpaired electrons. This diagram shows 8
electrons in bonding orbitals and 4 in antibonding orbitals, resulting in a predicted bond order
of 2.

We now turn to a molecular orbital description of the bonding in O 2. It so happens that the
molecular orbital description of this molecule provided an explanation for a long-standing puzzle
that could not be explained using other bonding models. To obtain the molecular orbital energy-
level diagram for O2, we need to place 12 valence electrons (6 from each O atom) in the energy-
level diagram shown in part (b) in Figure 9.8.19.8.1. We again fill the orbitals according to
Hund’s rule and the Pauli principle, beginning with the orbital that is lowest in energy. Two
electrons each are needed to fill the σ2s and σ2s* orbitals, 2 more to fill the σ2pzσ2pz orbital, and
4 to fill the degenerate π⋆2pxπ2px⋆ and π⋆2pyπ2py⋆ orbitals. According to Hund’s rule, the last
2 electrons must be placed in separate π * orbitals with their spins parallel, giving two unpaired
electrons. This leads to a predicted bond order of (8 − 4) ÷ 2 = 2, which corresponds to a double
bond, in agreement with experimental data (Table 4.5): the O–O bond length is 120.7 pm, and
the bond energy is 498.4 kJ/mol at 298 K.

-----Pi-molecular orbitals of butadiene and benzene.

 The number of pi molecular orbitals in the pi-system equals the number of

contributing atomic p orbitals. For butadiene (n=4) we saw that the energy levels of the
 pi system stacked like a four-story apartment building. Both hexatriene and benzene have
six contributing p-orbitals (n = 6), so we should expect six pi orbitals for each.

 The number of nodes increases with each successive energy level. A “node” is where
there is a change in phase between adjacent p-orbitals (i.e. where they can’t constructively
overlap). The lowest energy level (the “ground floor”, if you will) has all the p-orbitals
aligned the same way, and therefore has zero nodes between the p orbitals (not counting
the node inherent to the p-orbitals that lies in the plane of the molecule). This provides the
greatest possible delocalization of the electrons, and hence is the lowest in energy. Here’s
what the “ground floor” looks like for butadiene:

The highest
energy level (the “penthouse” of our building) has (n–1) nodes. We saw that for butadiene (n=4)
the highest energy level has three nodes between the orbitals (marked here with red lines).

The Ground Floor and the Penthouse are the easiest levels to draw, because they follow from
simple rules: align all phases, or alternate all phases.
-- aromaticity

In organic chemistry, the term aromaticity is used to describe a cyclic (ring-shaped), planar (flat)
molecule with a ring of resonance bonds that exhibits more stability than other geometric or
connective arrangements with the same set of atoms.

A property of some unusually stable organic molecules such as benzene. Although some
aromatic molecules are indeed fragrant (hello, vanillin! ) the term “aromaticity” actually has
nothing to do with smell. We saw that aromatic molecules:

 have an extremely high resonance energy (36 kcal/mol for benzene)

 undergo substitution rather than addition reactions

 have delocalized pi-electrons

-----Crystal field theory and the energy level diagrams for transition metal ions

and their magnetic properties

Crystal field theory (CFT) describes the breaking of orbital degeneracy in transition metal
complexes due to the presence of ligands. CFT qualitatively describes the strength of the metal-
ligand bonds. Based on the strength of the metal-ligand bonds, the energy of the system is
altered. This may lead to a change in magnetic properties as well as color. This theory was
developed by Hans Bethe and John Hasbrouck van Vleck [3].

In Crystal Field Theory, it is assumed that the ions are simple point charges (a simplification).
When applied to alkali metal ions containing a symmetric sphere of charge, calculations of bond
energies are generally quite successful. The approach taken uses classical potential energy
equations that take into account the attractive and repulsive interactions between charged
particles (that is, Coulomb's Law interactions).

E∝q1q2r(1)(1)E∝q1q2r

with

 EE the bond energy between the charges and

 q1q1 and q2q2 are the charges of the interacting ions and
 rr is the distance separating them.

This approach leads to the correct prediction that large cations of low charge, such
as K+K+ and Na+Na+, should form few coordination compounds. For transition metal cations
that contain varying numbers of d electrons in orbitals that are NOT spherically symmetric,
however, the situation is quite different. The shape and occupation of these d-orbitals then
becomes important in an accurate description of the bond energy and properties of the transition
metal compound.

-- the energy level diagrams for transition metal ions and their magnetic properties

The energy-level scheme and transition-selection rules for a transitional ion embedded into a
crystal host matrix are determined by the ion valence state, the structure and number of the
surrounding ligand ions. Besides, the valence and coordination of the optically active ions, the
quality of the crystals often determine the potential laser application. In the static crystal field
approach each ion is assumed to be fixed at a mean lattice position and the crystal field
experienced by a centre will reflect the symmetry of its environment. Several theoretical models
have been elaborated to describe the energy-level structure of transition metal ions in the
crystals; among them there are the ligand-field theory [5, 6] and the angular overlap model [7].
The ligand field theory describes the splitting of the free ion energy levels in a Coulomb field of
surrounding ligands, taking into account chemical bonds formation between the central ion and
ligands.

Magnetic properties
There are various substances which show magnetic behavior. We have substances that are
attracted by the magnetic field and are called paramagnetic. This phenomenon is called
paramagnetism. Paramagnetic property is only shown when the substance contains one or more
unpaired electrons. When a substance acquires a permanent magnetic moment, it is known as
ferromagnetic and the phenomenon is called ferromagnetism. On the other hand, we also have
substances which are repelled by magnetic field and are called as diamagnetic substances. A
substance shows diamagnetism when it contains only paired electrons.
Most of the transition elements show paramagnetic behavior. The unpaired electrons in (n-1) d
orbitals are responsible for the magnetic properties. The paramagnetic character of the transition
metals increases on moving from left to right as the number of unpaired electron increases from
one to five. The middle elements are found to possess the maximum paramagnetic property. The
magnetic properties decrease with the decrease in the number of unpaired electrons. The
transition metals which contain paired electrons depict diamagnetic behavior.
-- Band structure of solids and the role of doping on band structures.

the electronic band structure (or simply band structure) of a solid describes the range
of energies that an electron within the solid may have (called energy bands, allowed bands, or
simply bands) and ranges of energy that it may not have (called band gaps or forbidden bands).
Band theory derives these bands and band gaps by examining the allowed quantum
mechanical wave functions for an electron in a large, periodic lattice of atoms or molecules.
Band theory has been successfully used to explain many physical properties of solids, such
as electrical resistivity and optical absorption, and forms the foundation of the understanding of
all solid-state devices (transistors, solar cells, etc.).

Doping means the introduction of impurities into a semiconductor crystal to the defined
modification of conductivity. Two of the most important materials silicon can be doped with, are
boron (3 valence electrons = 3-valent) and phosphorus (5 valence electrons = 5-valent). Other
materials are aluminum, indium (3-valent) and arsenic, antimony (5-valent).

The dopant is integrated into the lattice structure of the semiconductor crystal, the number of
outer electrons define the type of doping. Elements with 3 valence electrons are used for p-type
doping, 5-valued elements for n-doping. The conductivity of a deliberately contaminated silicon
crystal can be increased by a factor of 106.

Electronic band structure in doped semiconductors

By the introduction of a dopant with five outer electrons, in n-doped semiconductors there is an
electron in the crystal which is not bound and therefore can be moved with relatively little energy
into the conduction band. Thus in n-doped semiconductors the donator energy level is close to
the conduction band edge, the band gap to overcome is very small.

Analog, through introduction of a 3-valent dopant in a semiconductor, a hole is available, which

may be already occupied at low-energy by an electron from the valence band of the silicon. For
p-doped semiconductors the acceptor energy level is close the valence band.
Band model of doped semiconductors